US2692277A - Manufacture of cyclohexanols and esters thereof, from isopropyl alcohol or secondary butyl alcohol - Google Patents
Manufacture of cyclohexanols and esters thereof, from isopropyl alcohol or secondary butyl alcohol Download PDFInfo
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- US2692277A US2692277A US158939A US15893950A US2692277A US 2692277 A US2692277 A US 2692277A US 158939 A US158939 A US 158939A US 15893950 A US15893950 A US 15893950A US 2692277 A US2692277 A US 2692277A
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- alcohol
- alkali metal
- reaction
- secondary butyl
- boiling
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 title claims description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical class OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title description 58
- 150000002148 esters Chemical class 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 238000009835 boiling Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- -1 cyclic alcohols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to the manufacture of cyclic alcohols and to esters thereof.
- the process for the preparation of cyclic alcohols comprises subjecting an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol in the liquid phase in the presence of alkali metal hydroxide or alkali metal alcoholate to temperatures in excess of 250 C.v and separating the cyclic alcohol produced from the reaction mixture.
- the cyclic alcohols may be esterified before or after separation from the reaction mixture, to give the corresponding esters.
- the separation of the cyclic alcohol from the reaction mixture may be effected by careful fractional distillation, preferably under diminished pressure, of the reaction mixture resulting from the condensation reaction.
- the cyclic alcohol is collected in that fraction which corresponds to its boiling point at the given pressure.
- This fraction if sufiiciently pure, may crystallise on cooling to room temperature or somewhat below room temperature. If necessary, or desired, this fraction may be subjected to further refractionation.
- the amount of alkali metal hydroxide or alkali metal alcoholate employed in the reaction is non-critical and may vary within Widelimits. Amounts of 1 to 10% of the alkali metal hydroxide or alcoholate calculated on the alcohol starting material give satisfactory results. It is prefered to use potassium hydroxide as the alkali metal hydroxide. It is to be noted that in place of using an alkali metal alcoholate per se, the alcohol starting material may be mixed with an alkali metal hydroxide and the mixture dehydrated for example by distillation in the presence of a small amount of benzene, and the resulting solution, which will contain the corresponding alkali metal alcoholate, used for the reaction.
- the temperature at which the reaction is carried out is advantageously between 250 and 300 C.
- the temperature employed must not be in excess of that at which the reaction mixture will no longer be in the liquid phase.
- the upper limit of the temperature which may be employed is accordingly the critical temperature of the liquid reaction mixture.
- the alcohol starting material may be subjected to the process of the invention either alone or in the presence of an inert solvent, which suitably reduces the pressure needed to maintain the alcohol in the liquid phase during the reaction, for example a hydrocarbon boiling appreciably above the boiling point of the alcohol being reacted.
- Methyl isobutyl carbinol is a suitable solvent when the alcohol starting material is isopropyl alcohol, and it is thus possible to recycle the methyl isobutyl carbinol which has been formed during the reaction or added initially together with unchanged isopropyl alcohol.
- the process according to the invention may preferably be carried out in metal vessels such as autoclaves of mild steel or stainless steel, or nickel lined vessels. It has been found useful to add to the reaction mixture small amounts of a finely divided metal, such as copper-bronze, for catalysing the condensation of the alcohol starting material.
- metal vessels such as autoclaves of mild steel or stainless steel, or nickel lined vessels. It has been found useful to add to the reaction mixture small amounts of a finely divided metal, such as copper-bronze, for catalysing the condensation of the alcohol starting material.
- the yield of the cyclic alcohol and the speed of the reaction varies according to conditions of the reaction such as pressures, temperatures and amounts of alkali metal hydroxide used.
- conditions of the reaction such as pressures, temperatures and amounts of alkali metal hydroxide used.
- increase in the pressure and/or temperature and/or amount of alkali will result in an increase in the speed of the reaction. It has further been ascertained that by increasing the total conversion of alcohol starting material, an increase in the yield of cyclic alcohol is obtained, at the expense of the lower boiling condensation products of the alcohol.
- the process of the invention thus leads in one single operation from isopropyl alcohol to 1:1:3- trimethylcyclohexanol-5, and, therefore, offers a very simple and cheap method for producing this compound which had hitherto been obtained only by the hydrogenationof isophorone.
- 1:1:3-tri methy1cyclohexanol-5 may be used as an intermediate for a number of compounds having very valuable properties; the use of isopropyl alcohol as the starting material thus constitutes an unexpected and cheap method of obtaining these compounds.
- the condensation; of. isobutyl-i' alcohol according to the present invention gives asubstituted cyclohexanol of 12 carbon atoms.
- Esterification of the cyclic alcohol can be effected with or without isolation of the cyclo-- hexanol from the condensation product by any method known or used in the art'for"the'esterification of alcohols.
- the 1:1:3- trimethylcyclohexanol-B prepared by the condensation of isopropyl alcohol may be treated with the anhydride of a carboxylic acid suitably in the presence of an esterification catalyst such: as sulphuric acid, or it may be treated with-the carboxylic acid in the presenceof an. esterifica' tion catalyst and suitably also in the presence:
- the present invention relates particularly to 1:'1:3- trimethyl-cyclohexyl-5 acetate and the monoand diestersof 1i:l:3-trimethylcyclohexanol+5 and phthalic acid, sebacic acid and .adipic. acid.
- Theesters of: 1:123+trimethylcyclohexanol-5. have valuable properties as plasticisers
- The: following. examples are given to. illustrate the process ofthe present invention. The per-'- centages' quoted are'by" weight unless'otherwise indicated.
- Example-1 In a'10-liter autoclave made-of stainless steel,
- a convenient way of isolating the 1:1:3-trimethylcyclohexanol-5 from the condensation products of isopropyl alcohol is to fractionate the reaction products after the removal of unchanged isopropanol and at least part of the methyl isobutyl carbinol, under reduced pressure, and collect. the fraction of the C9 range which has a density of more than 0.81 at 20 C.
- the condensation product is neutralised,, isopropyl alcohol and. methyl isobutylcarbinol removed as: az'eotropes with water' and, finally, the remainingoil layer fractionated at a pressure: of 17- mm. This: distillate comes over from 823 105 C.
- the feed enters atthetop of the tube at the rate of 150- millilitres per hour, and product'is removed, from.the-- base in such a way that a column of liquid reaction mixture is maintained in the heated reaction. tube, Provision is also made for separating;any. aqueous layer formedJby thereaction.
- the reactor is initially pressuri'sedito atmospheres pressure and maintained at; this. pressure. by venting the gas produced.
- a con stant temperature within the range.2503'00"C;, as indicated. in the table below' is used.
- the product obtained isi-distilled. in the presence of water. to remove first small amounts of hexenes and acetone,- followed by unchanged,
- isopropanol The aqueous layer. is thenseparated, and the oil residue distilled, yielding methyl isobutyl carbi'nol' (boiling point 40 5'0 C; at 10. millimetres. of" mercury), and 1':l:'3'-tri'- methylcyclohexanol 5,, (boiling point C..
- Example 6 200 grams of 1:1:3-trimethylcyclohexanol-5, prepared as in Example 1, 95 grams of sebacic acid, 47.5 grams of benzene and 0.18 grams of concentrated sulphuric acid are heated at a reaction temperature between 135 and 145 C. in an apparatus fitted with a Dean Stark head, the water being removed as an azeotrope with the benzene. The time taken for the reaction is 11 /2 hours. The product is washed with aqueous sodium carbonate to remove unchanged acid and the organic layer separated and fractionally distilled under reduced pressure. The di-lzlz3-trimethylcyclohexy1 5 sebacate, boiling at 220-225 C. at 0.2 millimetres of mercury is separated.
- the saponification value of the ester is 96.5% of the theoretical.
- Example 7 106.5 grams of 1:1:3trimethylcyclohexano1- 36.5 grams of adipic acid, 20 grams of benzene and 0.1 millilitre of concentrated sulphuric acid are admixed, and then heated under reflux, the water formed being removed by an azeotropio distillation head. After 2 hours, when the theoretical amount of water (9 millilitres) has been removed, the mixture is poured into 200 millilitres of 10% sodium carbonate solution and allowed to stand overnight. The benzene solution of the ester is washed with four 100 millilitre portions, stripped of benzene and water and then distilled and di(l:1:3-trimethy1cyclohexyl) adipate collected as a viscous liquid.
- Example 8 106.5 grams of 1:1:3-trimethylcyclohexanol-5, 37 grams of phthalic anhydride, grams of benzene and 0.1 millitre of concentrated sulphuric acid are admixed, and then heated under reflux, the water formed being removed by an azeotropic distillation head. After 2 hours, when the theoretical amount of Water (9 millilitres) has been removed, the mixture is poured into 200 millilitres of 10% sodium carbonate solution and allowed to stand overnight. The benzene solution of the ester is washed with four 100 millilitre portions, stripped of benzene and water and then distilled and di(l:1:3-trimethylcyclohexyl) phthalate collected as a viscous liquid.
- Example 9 400 grams of dry secondary butyl alcohol are heated with 57 grams of potassium hydroxide in a stainless steel autoclave for 4 hours at 250 C. At the termination of the reaction there is a pressure of atmospheres in the autoclave after cooling. The condensation reaction product is separated, washed with water, and distilled. The lower boiling fractions which are obtained comprise unchanged, secondary butyl alcohol, and then a fraction, boiling at 765 C. at 12.5 millimetres of mercury, comprising an octyl alcohol is obtained and finally a fraction boiling at 119-122 C. at 12 millimetres of mercury pressure is separated which comprises the substituted cyclohexanol of the formula 012E240. The purified alcohol boils at 120 C. at 10 mm. of mercury pressure. Oxidation of said alcohol yielded a ketone B. Pt. 111 C. at 10 mm. mercury pressure and the 2:4-dinitrophenylhydrazone derivative of this ketone had M. Pt. of 82 C.
- Example 10 Secondary butyl alcohol containing 15% Weight by volume of potassium secondary butylate is continuously pumped at 320 millilitres per hour into the upper end of a tubular reactor, 660 millilitres in volumes, which is electrically heated to 254-266 C. and pressurised with nitrogen to pounds per square inch gauge. lfhis pressure was maintained by the release of hydrogen through a needle valve at the rate at which it was formed in the reaction. The product is removed continuously from the lower end of the reactor through a constant level siphon tube, which serves to maintain a column of the liquid reaction mixture in the reactor, and is collected in a pressurised receiver.
- the product after washing with water to remove potash and potas--' sium salts, is distilled to separate the unchanged secondary butyl alcohol, and then fractionated, giving a fraction boiling between 75 and 89 C. at 27 millimeters of mercury, which contains an octyl alcohol, and then a fraction boiling between and 138 C. at 16 millimetres of mercury pressure.
- a fraction boiling at -132 C. at 16 millimetres of mercury comprising a substituted cyclohexanol of the formula 012K240 is separated.
- This substituted cyclohexanol has a density d4 of 0.9081 and a refractive index 11 of 1.4729.
- a process for the preparation of a cyclohexanol which comprises the step of condensing an alcohol selected from the group consisting of isoprop-yl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in the range of about 250 C. to 300 C. in the presence of an alkaline material selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol, whereby the corresponding cyclohexanol is produced.
- a process for the preparation of cyclohexanols which comprises condensing an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in excess of 250 C. in the presence of an alkaline material selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol and thereafter distilling the reaction mixture to separate the cyclohexanol produced.
- a process for the preparation of cyclohexanols which comprises condensing an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in the range or" about 250 C. to 300 C. in the presence of a member selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol, and thereafter distilling the reaction mixture to separate the cyclohexanol produced.
- a process for the preparation of cyclohexanols which comprises admixing an alkali metal hydroxide with an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, dehydrating the mixture, then heating said mixture to a temperature in the range of about 250 C. to 300 0., and
- a process for the preparation of 1:1:"3-"trimethylcyclohexanol-5 which comprises condensing isopropyl alcohol by heating in the liquid phase to a temperature in the range of about 250 C. to 300 C. in the presence of an alkaline mate rial selected .from the group consisting .of alkali metal hydroxide and. alkali metal 'isopropylate and thereafter separating from the reaction mixture the 1:1z3-trimethylcyclohexanol-5 produced.
- an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol
Description
Patented Oct. 19, 1954 UNITED STAT S PATENT OFFICE William Edgar Nelson, Newport, Wales, assignor to The Bistillers Company Limited, Edinburgh, Scotland, a British company No Drawing. Application April 28, 1950, Serial No. 158,939
Claims 'priority, application Great Britain May 6, 1949 6 Claims.
The present invention relates to the manufacture of cyclic alcohols and to esters thereof.
According to the invention the process for the preparation of cyclic alcohols comprises subjecting an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol in the liquid phase in the presence of alkali metal hydroxide or alkali metal alcoholate to temperatures in excess of 250 C.v and separating the cyclic alcohol produced from the reaction mixture. The cyclic alcohols may be esterified before or after separation from the reaction mixture, to give the corresponding esters.
The separation of the cyclic alcohol from the reaction mixture may be effected by careful fractional distillation, preferably under diminished pressure, of the reaction mixture resulting from the condensation reaction. On distilling, advantageously after previous neutralisation, first unchanged alcohol distills over, then any low boiling products, such for example as methyl isobutyl carbinol, which is also formed by the condensation of isopropanol, which may be formed during the heating. Finally the cyclic alcohol is collected in that fraction which corresponds to its boiling point at the given pressure. This fraction, if sufiiciently pure, may crystallise on cooling to room temperature or somewhat below room temperature. If necessary, or desired, this fraction may be subjected to further refractionation.
The amount of alkali metal hydroxide or alkali metal alcoholate employed in the reaction is non-critical and may vary within Widelimits. Amounts of 1 to 10% of the alkali metal hydroxide or alcoholate calculated on the alcohol starting material give satisfactory results. It is prefered to use potassium hydroxide as the alkali metal hydroxide. It is to be noted that in place of using an alkali metal alcoholate per se, the alcohol starting material may be mixed with an alkali metal hydroxide and the mixture dehydrated for example by distillation in the presence of a small amount of benzene, and the resulting solution, which will contain the corresponding alkali metal alcoholate, used for the reaction. The temperature at which the reaction is carried out is advantageously between 250 and 300 C. The temperature employed must not be in excess of that at which the reaction mixture will no longer be in the liquid phase. The upper limit of the temperature which may be employed is accordingly the critical temperature of the liquid reaction mixture. In order to maintain the alcohol during the reaction in the liquid phase the reaction'is carried out under pressure. During the reaction, which may be efiected either batchwise or as a continuous process, hydrogen is liberated.
The alcohol starting material may be subjected to the process of the invention either alone or in the presence of an inert solvent, which suitably reduces the pressure needed to maintain the alcohol in the liquid phase during the reaction, for example a hydrocarbon boiling appreciably above the boiling point of the alcohol being reacted. Methyl isobutyl carbinol is a suitable solvent when the alcohol starting material is isopropyl alcohol, and it is thus possible to recycle the methyl isobutyl carbinol which has been formed during the reaction or added initially together with unchanged isopropyl alcohol.
The process according to the invention may preferably be carried out in metal vessels such as autoclaves of mild steel or stainless steel, or nickel lined vessels. It has been found useful to add to the reaction mixture small amounts of a finely divided metal, such as copper-bronze, for catalysing the condensation of the alcohol starting material.
The yield of the cyclic alcohol and the speed of the reaction varies according to conditions of the reaction such as pressures, temperatures and amounts of alkali metal hydroxide used. Thus, for example, increase in the pressure and/or temperature and/or amount of alkali will result in an increase in the speed of the reaction. It has further been ascertained that by increasing the total conversion of alcohol starting material, an increase in the yield of cyclic alcohol is obtained, at the expense of the lower boiling condensation products of the alcohol.
starting material. It is, therefore, a preferred method of carrying out the process of the invention by condensing more than 20% of the alcohol introduced.
The condensation of isopropyl alcohol according to the present invention gives 1:1 :3-trimethy1cyclohexanol-5.
The process of the invention thus leads in one single operation from isopropyl alcohol to 1:1:3- trimethylcyclohexanol-5, and, therefore, offers a very simple and cheap method for producing this compound which had hitherto been obtained only by the hydrogenationof isophorone. 1:1:3-tri methy1cyclohexanol-5 may be used as an intermediate for a number of compounds having very valuable properties; the use of isopropyl alcohol as the starting material thus constitutes an unexpected and cheap method of obtaining these compounds.
The condensation; of. isobutyl-i' alcohol according to the present invention gives asubstituted cyclohexanol of 12 carbon atoms.
Esterification of the cyclic alcohol can be effected with or without isolation of the cyclo-- hexanol from the condensation product by any method known or used in the art'for"the'esterification of alcohols. Thus for example the 1:1:3- trimethylcyclohexanol-B prepared by the condensation of isopropyl alcohol may be treated with the anhydride of a carboxylic acid suitably in the presence of an esterification catalyst such: as sulphuric acid, or it may be treated with-the carboxylic acid in the presenceof an. esterifica' tion catalyst and suitably also in the presence:
of a water entrainer such as benzene. The present invention relates particularly to 1:'1:3- trimethyl-cyclohexyl-5 acetate and the monoand diestersof 1i:l:3-trimethylcyclohexanol+5 and phthalic acid, sebacic acid and .adipic. acid. Theesters of: 1:123+trimethylcyclohexanol-5. have valuable properties as plasticisers The: following. examples are given to. illustrate the process ofthe present invention. The per-'- centages' quoted are'by" weight unless'otherwise indicated.
Example-1 In a'10-liter autoclave made-of stainless steel,
mal pressure, contain the unconverted isopropyl.
alcohol, and the fractionboiling between 88 and 97 C. contains themethyl'isobutylcarbinol water constant boiling mixture. The oiliin. the still kettle is now eparated from the water. and fractionated separately at 16-20 mm-. pressure. A. fraction boiling between 85 and.110' C. at I6 mm. is. collected and is identified as almost pure.
1 :1:3-trimethylcyclohexanol-5. Itv crystallises on standing and is purifiedby a refractionation. The main fraction comes at normal pressure. over at 196.5l98 Chat 742 mm. and the crys tals of the distillate have a melting. point of'32.5 C. In the above experiment of theoriginal isopropanol is converted,.29.8% going. to methyl isobutyl carbinol, 11%". to trimethylc'yclohexanol' and 4.1% to a mixture of C9 and C12 alcohols. 4.2% of the potassium hydroxide originally added, is converted to other compounds during the reaction.
A convenient way of isolating the 1:1:3-trimethylcyclohexanol-5 from the condensation products of isopropyl alcohol is to fractionate the reaction products after the removal of unchanged isopropanol and at least part of the methyl isobutyl carbinol, under reduced pressure, and collect. the fraction of the C9 range which has a density of more than 0.81 at 20 C. Thus, in one experiment the condensation product is neutralised,, isopropyl alcohol and. methyl isobutylcarbinol removed as: az'eotropes with water' and, finally, the remainingoil layer fractionated at a pressure: of 17- mm. This: distillate comes over from 823 105 C. It possesses aspecificgravity of 0.921 at' 15- C. The fraction solidifies when cooled below 15 C. 0n retrac tionation pure 1:1:3-trimethylcyclohexanol-5 is obtained, having a boiling point of 196 C. at 752 The specificitgravitye'ofithis alcoholiis 0.887 at 37 (3'.
Examples 2-4 Isopropyl alcohol containing 8% by weight of potassium. hydroxide. is mixed with a little benzene and'dehyd-rated' in a still, by removing continuously the lower layer of the ternary azeotrope which. distil's. The resulting solution, in which more than half of the potassium hydroxide has been converted to potassium isopropylate is pumped continuously to the reactor, which consists: of a heated vertical stainless steel tube, of
inch bore and 300 millilitres capacity. The feed enters atthetop of the tube at the rate of 150- millilitres per hour, and product'is removed, from.the-- base in such a way that a column of liquid reaction mixture is maintained in the heated reaction. tube, Provision is also made for separating;any. aqueous layer formedJby thereaction. The reactor is initially pressuri'sedito atmospheres pressure and maintained at; this. pressure. by venting the gas produced. A con: stant temperature within the range.2503'00"C;, as indicated. in the table below' is used.
The product obtained isi-distilled. in the presence of water. to remove first small amounts of hexenes and acetone,- followed by unchanged,
isopropanol. The aqueous layer. is thenseparated, and the oil residue distilled, yielding methyl isobutyl carbi'nol' (boiling point 40 5'0 C; at 10. millimetres. of" mercury), and 1':l:'3'-tri'- methylcyclohexanol 5,, (boiling point C..
Refractionation.
at lomillimetres of mercury); of the latter gives pure 1'11:3 trimetliylcyclohexanol-S', (boiling point 90'-I00' Cf; at 10" mini metres of mercury), which crystallise's on cool- The results. obtained. in. these. examples. are given in the. following. table;
| Percent. l tfiltiti" yield ifit-i Example gfi s g' sion*of Xnethyl 9., glgggpyl 057010112X isoliutyl anom car 1110- 1 2501 30. 1*. 31.17 ll 3958. 274 as. 5 37. 7 20. 5 29B 39. 6 40'. 9 11. 5
Eitample. 5.
In; a Ill-litre autoclave madeof: stainless steel,-
5 litres of dry isopropanol containing 8% potassium hydroxide: is heated to 290 C; for' 4- hours. The. liquid reaction product is washed with a small amount of water-andthe top layer n'eutralis'ed with acetic acid and then-fi'a'ction-- ated in the presence of water. The lowest boil ing fraction contains some olefine. The next-- fraction, boiling between 78 C. and 88"" C; at normal pressure; contains the unconverted iso.-- propanol, and: the fraction boiling between 88 and 97 C. containsthe methyl isobutyl carbinolwater constant boiling mixtures The oil in the. still. kettle is now separated from the-water andt fractionated separately at: 16-20. mmpressure. A. fraction boiling between.- 85. and C. at 116'. mm. is: collected. and identified as almost pure- 1 1.: 3-trimethylcyclohexanoli The pure 1':1.:3-trimethylcycloi1exanol-5; thus obtained is heated with: a'ceticanhydride. and a. trace: of sulphuric acid; The: product obtained: is fractionally distilled and the 1:1:3:-trimethyl.--
m Amok! cyclohexyl acetate, boiling at 210 C. at normal pressure, separated.
Example 6 200 grams of 1:1:3-trimethylcyclohexanol-5, prepared as in Example 1, 95 grams of sebacic acid, 47.5 grams of benzene and 0.18 grams of concentrated sulphuric acid are heated at a reaction temperature between 135 and 145 C. in an apparatus fitted with a Dean Stark head, the water being removed as an azeotrope with the benzene. The time taken for the reaction is 11 /2 hours. The product is washed with aqueous sodium carbonate to remove unchanged acid and the organic layer separated and fractionally distilled under reduced pressure. The di-lzlz3-trimethylcyclohexy1 5 sebacate, boiling at 220-225 C. at 0.2 millimetres of mercury is separated.
The saponification value of the ester is 96.5% of the theoretical.
Example 7 106.5 grams of 1:1:3trimethylcyclohexano1- 36.5 grams of adipic acid, 20 grams of benzene and 0.1 millilitre of concentrated sulphuric acid are admixed, and then heated under reflux, the water formed being removed by an azeotropio distillation head. After 2 hours, when the theoretical amount of water (9 millilitres) has been removed, the mixture is poured into 200 millilitres of 10% sodium carbonate solution and allowed to stand overnight. The benzene solution of the ester is washed with four 100 millilitre portions, stripped of benzene and water and then distilled and di(l:1:3-trimethy1cyclohexyl) adipate collected as a viscous liquid.
Example 8 106.5 grams of 1:1:3-trimethylcyclohexanol-5, 37 grams of phthalic anhydride, grams of benzene and 0.1 millitre of concentrated sulphuric acid are admixed, and then heated under reflux, the water formed being removed by an azeotropic distillation head. After 2 hours, when the theoretical amount of Water (9 millilitres) has been removed, the mixture is poured into 200 millilitres of 10% sodium carbonate solution and allowed to stand overnight. The benzene solution of the ester is washed with four 100 millilitre portions, stripped of benzene and water and then distilled and di(l:1:3-trimethylcyclohexyl) phthalate collected as a viscous liquid.
Example 9 400 grams of dry secondary butyl alcohol are heated with 57 grams of potassium hydroxide in a stainless steel autoclave for 4 hours at 250 C. At the termination of the reaction there is a pressure of atmospheres in the autoclave after cooling. The condensation reaction product is separated, washed with water, and distilled. The lower boiling fractions which are obtained comprise unchanged, secondary butyl alcohol, and then a fraction, boiling at 765 C. at 12.5 millimetres of mercury, comprising an octyl alcohol is obtained and finally a fraction boiling at 119-122 C. at 12 millimetres of mercury pressure is separated which comprises the substituted cyclohexanol of the formula 012E240. The purified alcohol boils at 120 C. at 10 mm. of mercury pressure. Oxidation of said alcohol yielded a ketone B. Pt. 111 C. at 10 mm. mercury pressure and the 2:4-dinitrophenylhydrazone derivative of this ketone had M. Pt. of 82 C.
6 Example 10 Secondary butyl alcohol containing 15% Weight by volume of potassium secondary butylate is continuously pumped at 320 millilitres per hour into the upper end of a tubular reactor, 660 millilitres in volumes, which is electrically heated to 254-266 C. and pressurised with nitrogen to pounds per square inch gauge. lfhis pressure was maintained by the release of hydrogen through a needle valve at the rate at which it was formed in the reaction. The product is removed continuously from the lower end of the reactor through a constant level siphon tube, which serves to maintain a column of the liquid reaction mixture in the reactor, and is collected in a pressurised receiver. The product, after washing with water to remove potash and potas--' sium salts, is distilled to separate the unchanged secondary butyl alcohol, and then fractionated, giving a fraction boiling between 75 and 89 C. at 27 millimeters of mercury, which contains an octyl alcohol, and then a fraction boiling between and 138 C. at 16 millimetres of mercury pressure. On refractionation of this last fraction, a fraction boiling at -132 C. at 16 millimetres of mercury comprising a substituted cyclohexanol of the formula 012K240 is separated. This substituted cyclohexanol has a density d4 of 0.9081 and a refractive index 11 of 1.4729.
1: 1 3-trimethylcyclohexanol-5 possesses valuable solvent properties, and can be used to advantage to replace other alcohol solvents in their uses in various fields.
I claim:
1. A process for the preparation of a cyclohexanol, which comprises the step of condensing an alcohol selected from the group consisting of isoprop-yl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in the range of about 250 C. to 300 C. in the presence of an alkaline material selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol, whereby the corresponding cyclohexanol is produced.
2. A process for the preparation of cyclohexanols which comprises condensing an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in excess of 250 C. in the presence of an alkaline material selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol and thereafter distilling the reaction mixture to separate the cyclohexanol produced.
3. A process for the preparation of cyclohexanols Which comprises condensing an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in the range or" about 250 C. to 300 C. in the presence of a member selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol, and thereafter distilling the reaction mixture to separate the cyclohexanol produced.
l. A process for the preparation of cyclohexanols which comprises admixing an alkali metal hydroxide with an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, dehydrating the mixture, then heating said mixture to a temperature in the range of about 250 C. to 300 0., and
from the reaction mixture.
5. A process for the preparation of 1:1:"3-"trimethylcyclohexanol-5 which comprises condensing isopropyl alcohol by heating in the liquid phase to a temperature in the range of about 250 C. to 300 C. in the presence of an alkaline mate rial selected .from the group consisting .of alkali metal hydroxide and. alkali metal 'isopropylate and thereafter separating from the reaction mixture the 1:1z3-trimethylcyclohexanol-5 produced.
6. In a process tor the preparation of esters of cyolohexanols, theJsteps of condensing an alcohol selected from the group consisting of isopropyl alcohol and secondary butyl alcohol, by heating in the liquid phase to a temperature in excess of 250 C. in the presence of an alkaline material selected from the group consisting of alkali metal hydroxide and alkali metal alcoholate of the involved alcohol, whereby the corresponding cyclohexanol is produced thereafter esterif-ying the cyclchexanol thus produced without septum tion thereof from the reaction mixture, and thereafter separating the resultant ester.
References Cited in the file of this patent UNITED STATES PATENTS Number Name 'Date 1,797,612 Jordan a Mar. 24, 1 931 1,841,430 Bollmarm Jan. 19., 1932 1,923,938 Ky-rides Aug-22,11 933 2,026,668 Bruson-et a1 Jan. "7, 1936 2,403,804 Kesslin et al. July 9, 1946 2,451,739 Isler Oct. 11:94, 1948 2,473,544 :Rehb'erg et al. -June:21,1949 2,497,433 'B1ak'e Feb. 14, 1951) 2,499,848 Catlin et a1 7, 1950 OTHER REFERENCES LII-ch
Claims (1)
1. A PROCESS FOR THE PREPARATION OF A CYCLOHEXANOL, WHICH COMPRISES THE STEP OF CONDENSING AN ALCOHOL SELECTED FROM THE GROUP CONSISTING OF ISPROPYL ALCOHOL AND SECONDARY BUTYL ALCOHOL, BY HEATING IN THE LIQUID PHASE TO A TEMPERATURE IN THE RANGE OF ABOUT 250* C. TO 300* C. IN THE PRESENCE OF AN ALKALINE MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDE AND ALKALI METAL ALCOHOLATE OF THE INVOLVED ALCOHOL, WHEREBY THE CORRESPONDING CYCLOHEXANOL IS PRODUCED.
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US158939A Expired - Lifetime US2692277A (en) | 1949-05-06 | 1950-04-28 | Manufacture of cyclohexanols and esters thereof, from isopropyl alcohol or secondary butyl alcohol |
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US3163113A (en) * | 1959-01-12 | 1964-12-29 | Burke | High energy fuel units and assemblies |
US4827019A (en) * | 1985-12-24 | 1989-05-02 | Eastman Kodak Company | Sterically hindered aromatic carboxylic esters |
EP1298121A1 (en) * | 2000-07-03 | 2003-04-02 | Daicel Chemical Industries, Ltd. | Bis(cis-3,3,5-trimethylcyclohexyl) phthalate, process for producing the same, and thermoplastic resin composition |
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US4827019A (en) * | 1985-12-24 | 1989-05-02 | Eastman Kodak Company | Sterically hindered aromatic carboxylic esters |
EP1298121A1 (en) * | 2000-07-03 | 2003-04-02 | Daicel Chemical Industries, Ltd. | Bis(cis-3,3,5-trimethylcyclohexyl) phthalate, process for producing the same, and thermoplastic resin composition |
EP1298121A4 (en) * | 2000-07-03 | 2005-10-05 | Daicel Chem | Bis(cis-3,3,5-trimethylcyclohexyl) phthalate, process for producing the same, and thermoplastic resin composition |
JP4768953B2 (en) * | 2000-07-03 | 2011-09-07 | ダイセル化学工業株式会社 | Bis (cis-3,3,5-trimethylcyclohexyl) phthalate, method for producing the same, and thermoplastic resin composition |
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